New hair dyeing solution

ABSTRACT

A COMPOSITION FOR DYEING KERATINIC FIBERS COMPRISING EFFECTIVE AMOUNTS OF AROMATIC PARADIAMINE OF THE FORMULA   1,4-DI(H2N-),2,6-DI(R-),3-(CH3-O-)BENZENE   IN WHICH R AND R&#39;&#39; EACH REPRESENT A SUBSTANCE SELECTED FROM THE GROUP CONSISTING OF HYDROGEN AND METHYL, BUT R&#39;&#39; MUST BE METHYL WHEN R IS METHYL, AND META-AMINO-PHENOL WHICH SERVES AS A COUPLING SUBSTANCE OF THE FORMULA   3-(R2-NH-),4-CH3,6-R1-PHENOL   IN WHICH R1 REPRESENTS A SUBSTANCE SELECTED FROM THE GROUP CONSISTING OF CHLORINE AND HYDROGEN AND R2 REPRESENTS A SUBSTANCE SELECTED FROM THE GROUP CONSISTING OF HYDROGEN, CARBOMAYLMETHYL AND DIETHYL CARBAMYLMETHYL, BUT R1 MUST BE CHLORINE WHEN R2 IS HYDROGEN, AND THE METHOD OF DYEING HAIR WITH THIS COMPOSITION.

United States Patent Int. Cl. $61k 7/12 U.S. Cl. 3-11 17 Claims ABSTRACTOF THE DISCLOSURE A composition for dyeing keratinic fibers comprisingelfective amounts of aromatic paradiamine of the formula in which R andR each represent a substance selected from the group consisting ofhydrogen and methyl, but R must be methyl when R is methyl; andmeta-amino-phenol which serves as a coupling substance of the formulaHair dyes having a substituted or unsubstituted ,aromatic diamine basehave been used for a long time. The substitutions are carried by thearomatic ring or the nitrogen atoms of the amino groups. Couplingsubstances are added to these diamines to vary the color obtained.

It is also known that the addition of certain coupling substances tosuch aromatic paradiamines makes it possible to obtain particularlystable and long-lasting colorations, whereas the shades obtained withthe bases alone change rapidly. Moreover, certain of these bases are notdyes in themselves, but are effective only when suitably coupled.

Among the known substances conventionally coupled with aromaticparadiamines is meta-amino-phenol, which unfortunately frequentlyproduces hair dyes which do not last very long. The present inventionproposes a new class of meta-amino-phenols for use as couplingsubstances, which make it possible to obtain especially stablelonglasting colorations, which resist exposure to the light and tooutside agents, and enlarge the range of shades in the blue section ofthe spectrum which may be obtained by associating an aromaticparadiamine and a meta-aminophenol.

The object of the present invention is to provide a new dye forkeratinic fibers, and particularly for hair, essentially characterizedby the fact that it comprises, on the 3,591,323 Patented July 6, 1971Ice one hand, at least one aromatic paradiamine having the formula:

OCHai IHg I in which R and R represent hydrogen or a methyl radical, butR cannot be hydrogen when R is a methyl radical, and at least onemeta-amino-phenol serving as a coupling substance and having thefollowing formula:

| CH3 II in which R, is chlorine or hydrogen and R represents hydrogen,a carbamylmethyl radical, or a diethyl carbamylmethyl radical, but R maybe chlorine only when R is hydrogen.

The present invention is also directed to the new chemical compoundhaving the formula:

6H3 III in which R represents chlorine and R hydrogen, or R representshydrogen and R, a carbamylmethyl or diethylcarbamylmethyl radical.

A characteristic feature of the invention resides in the fact that inthe dyeing solution the ratio between the molecular concentration of thebases used and that of the coupling substances used is generally closeto, but preferably less than 1.

The said dyeing solution is utilized in a conventional manner, bybringing it to an alkaline pH, with ammonia, for example, and applyingit to the hair in the presence of an oxidizing solution, and preferablya hydrogen peroxide solution.

The dyeing solution may also contain other dyes which may be used underthe same conditions as direct dyes for keratinic fibers, for example azoor anthraquinone dyes, or dyes obtained by associating bases andcoupling substances other than those with which the present invention isconcerned.

The dyeing solutions may also contain wetting, dispersing, orpenterating agents, and other ingredients commonly included in hairdyes. The product may take the form of an aqueous solution, a cream or agel.

A very broad range of colors within the blue portion of the spectrum maybe obtained by associating a coupling substance according to theinvention with an aromatic paradiamine, and when an aromatic paradiamineis used with a combination of two coupling substances according to theinvention all the shades between those which can be obtained byassociating any of the single coupling substances with the base may besecured by varying the proportion between the two coupling substances.

Another object of the invention is the new method of dyeing the hairwhich comprises the steps of adding hydrogen peroxide, applying a dye ofthe above-defined type, and then rinsing, shampooing, washing and dryingthe hair.

EXAMPLE 4 Preparation of 2-amino-4-hydroxy-5-chlorotoluene This processembodies the reaction shown in the following diagram:

0.5 mol (76.5 g.) of 2-nitro-4-hydroxy toluene is reduced with a mixtureof tin and concentrated hydrochlo ric acid. This is filtered While hot,yielding 45 g. of 2- amino-4-hydroxy-5-chloro toluene hydrochloride,which is insoluble in concentrated hot hydrochloric acid. Thehydrochloric solution of the reduction contains 2-amino- 4-hydroxytoluene as chlorostannate. 2-amino-4-hydroxy toluene, which melts at 159C., may be isolated, if de sired.

The hydrochloride thus obtained is dissolved in water. The solution isalkalized with ammonia and drying yields 33.8 g. of2-amino-4-hydroxy-5-chloro toluene, which after recrystallization inbenzene, melts at 144.5 C.

Analysis.-Calculated for CqHgONCl (percent): C, 53.33; H, 5.07; N, 8.88.Found (percent): C, 53.33- 53.60; H, 5.08-5.02; N, 9.07-8.03.

EXAMPLE 5 The following solution is prepared:

2-amino-4-hydroxy-5-chloro toluene0.32 g.

2,5-diamino-4-methyl-l-methoxy benzene dihydrochloride-0.45 g.

Ammonium lauryl sulfate (having 20% fatty alcohol)--l0.00 g.

Ammonia (at 20% )7 cm.

Water, q.s.p. 100 g.

This solution is mixed with an equal weight of hydrogen peroxide at 20volumes, and applied to white hair. After 20 minutes, the hair isshampooed, rinsed and dried. An intense violet shade results.

EXAMPLE 6 The following solution is prepared:

1-hydroxy-4-methyl-S-carbamylmethylamino benzene-0,36 g.

2,5-diamino-4-methyl-l-methoxy benzene dihydrochloride0.39 g.

Ammonium lauryl sulfate (having 20% fatty alcohol)l0.00 g.

Ammonia at 20%-7 cm.

Water, q.s.p. 100 g.

This solution is mixed with an equal weight of hydrogen peroxide at 20volumes and applied to white hair. After 20 minutes, the hair isshampooed, rinsed, and dried. An intense, slightly violet, blue results.

EXAMPLE 7 The following solution is prepared:

2-amino-4-hydroxy toluene1.2 g. Paradiaminoanisol sulfate1.4 g. Ammoniaat 20%-10 cm. Alcohol at 95 10 cm.

Water, q.s.p. 100 cm.

This solution is mixed with an equal volume of hydrogen peroxide at 20volumes, and applied to 100% white hair. After 20 minutes, the hair isshampooed, washed, and dried. A strong marine blue shade, which isstable when exposed to the light, results.

6 EXAMPLE 8 The following solution was prepared:

2-amino-4-hydroxy-5-chloro toluene-15 g. 3,6-diamino-2,4-dimethyl anisoldihydrochloride-2.2 g. Ammonia at 20%-1O cm.

Water, q.s.p. 100 cm.

This solution is mixed with an equal volume of hydrogen peroxide at 20volumes. The mixture is applied to 100% white hair. After 20 minutes thehair is shampooed, rinsed, and dried. An intense bluish violet shade,which is stable when exposed to the light, results.

EXAMPLE 9 The following solution is prepared:

Z-carbomylmethylamino,4-hydroxy toluene-1.8 g. 2,5-diamino-4-methylanisol dihydrochloride-2.2 g. Ammonia at 20 %l0 cm.

Alcohol at 95 10 cm.

Water, q.s.p.-100 cm.

This solution is mixed with an equal volume of hydrogen peroxide at 20volumes. The mixture is applied to 50% white hair. After 20 minutes ofapplication the hair is shampooed, rinsed and dried. A deep blue-blackshade, which is stable when exposed to the light, results.

EXAMPLE 10 The following solution is prepared:

2-carbamylmethylamino-4-hydroxy toluene-4.8 g.Para-aminodiphenylaminel.8 g.

Ammonia at 20%-10 cm.

Alcohol at 95 -l0 cm.

Water, q.s.p.100 cm.

This solution is mixed with an equal volume of hydrogen peroxide at 20volumes and applied to white hair. After 30 minutes the hair isshampooed, rinsed and dried. A clear rosy chestnut shade, which isstable when exposed to the light, is obtained.

EXAMPLE 11 The following solution is prepared:

3,6-diamino-2,4-dimethyl anisol dihydrochl0ridel6.6 g.2-amino-4-hydroxy-5-chlorotoluene-1 5 .75 g. Ammonium lauryl sulfate at20%-200 g. Carboxymethylcellulose-20 g.

Sodium bisulfite-4 g.

Ethylene diamino tetra-acetic acid3 g.

Ammonia at 20%-100 cm.

Water, q.s.p.l000 g.

This mixture is a thick liquid. It is diluted, when used, with an equalvolume of hydrogen peroxide and applied to White hair. After 30 minutesthe hair is rinsed, shampooed, and dried. An intense violine shade,which is stable when exposed to the light, results.

EXAMPLE 12 The following solution is prepared:

The solution is a thick liquid. It is mixed with an equal volume ofhydrogen peroxide at 20 volumes and applied to 90% 'white hair. After 30minutes, the hair is rinsed, shampooed and dried. The result is aperiwinkle violet color, which is stable when exposed to the light.

7 EXAMPLE 13 The following solution is prepared:

3,6-diamino-2,4-dimethyl anisol dihydrochloride-83 g.

2-amino-4-hydroxy-5-chloro toluene7.8 g.

Ammonium lauryl sulfate at 20% 200 g.

Carboxymethylcellulose20 g.

Disodium salt of ethylene diamino tetraacetic acid (Trilon Sodiumbisulfite4 g.

Ammonia at 20%l00 cm.

Water, q.s.p.--1000 g.

This solution is mixed with an equal volume of hydrogenperoxide at 20volumes and applied to 90% white hair; After wating 30 minutes the hairis rinsed, shampooed and dried. The result is a mahogany violine shade,which is stable when exposed to the light.

EXAMPLE 14 The following solution is prepared:

The following solution is prepared:

Paradiamino anisol sulfate13.8 g.

Z-carbamylmethylamino-4-hydroxy toluenel8 g.

l-arniuo 2 nitro 4 amino aminoethyl benzene sulfate-2 g.

Ammonium lauryl sulfate at 20%200 g.

Carboxymethylcellulose-10 g.

Disodium salt of ethylene diamino tctraacetic acid (Trilon Ammonia at%-100 cm.

Water, q.s.p.l000 g.

This solution is mixed with an equal volume of hydrogen peroxide at 20volumes and applied to 90% 'White hair. After waiting minutes the hairis rinsed, shampooed and dried. The result is a mahogany violine shade,which is stable when exposed to the light.

EXAMPLE 16 The following solution is prepared:

Paradiamino-anisol sulfate13.8 g.

2-(diethylcarbamyl) methylamino 4 hydroxytoluene--18 g.

1-amino-2-nitro-4-amino-ethylamine benzene sulfate2 g.

Ammonium lauryl sulfate at 20%-200 g.

Carboxymethyl cellulose10 g.

Disodium salt of ethylene diamino tetraacetic acid (Trilon Sodiumbisulfite-4 g.

Ammonia at 20%100 crn.

Water, q.s.p.1000 g.

This solution is mixed with an equal volume of hydrogen peroxide at 20volumes and applied to 90% white hair. The result is a blue-black shadewhich is stable when exposed to the light.

It will be appreciated that the methods of carrying out Fit theinvention which have just been described have been given purely by wayof example and that the scope of the invention should not be consideredto be limited to the specific methods described.

In particular, it is obvious that the invention is not limited to theconcept of applying to the hair a dye containing simultaneously one ormore of the bases, one or more of the coupling substances and hydrogenperoxide, but that a plurality of solutions, each containing only one ormore of the various ingredients may be successively applied to the hair.

What is claimed is:

1. An aqueous composition for dyeing keratinic fibers comprising adyeing amount of (1) an aromatic paradiamine having the formula in whichR and R are selected from the group consisting of hydrogen and methyl,but R must be methyl when R is methyl, and (2) meta-amino-phenol whichserves as a coupling substance having the formula in which R representsa substance selected from the group consisting of chlorine and hydrogenand R represents a substance selected from the group consisting ofhydrogen, carbamylmethyl, and diethyl carbamylmethyl, but 'R is chlorineonly when R is hydrogen wherein the molar ratio of the aromaticparadiamine to said meta-amino-phenol is about 1 to 1.

2. The composition of claim 1 having a pH between 7 and 12.

13. The composition of claim 1 having a pH between 8 an 10.

4. The composition of claim 1, wherein said paradiamine is2,5-diamino-4-methyl-1-methoxy benzene dihydrochloride and saidmeta-amino-phenol is 2-amin0-4-hydroxy-S-chlorotoluene.

5. The composition of claim 1, wherein said paradiamine is2,5-diamino-4-methyl-1-methoxy benzene dihydrochloride and saidmeta-amino-phenol is 1-hydroxy-4-methyl-S-carbamylmethylamino benzene.

6. The composition of claim 1, wherein said paradiamine isparadiaminoanisol sulfate and said meta-aminophenol is 2-amino-4-hydroxytoluene.

7. The composition of claim 1, wherein said paradiamine is3,6-diamino-2,4-dimethyl-anisol dihydrochloride and saidmeta-amino-phenol is 2-amino-4-hydroxy-5-ch1orotoluene.

8. The composition of claim 1, wherein said paradiam1ne is2,5-diamino-4-methyl anisol dihydrochloride and said meta-amino-phenolis 2-carbamyl-methylamino-4-hydroxy toluene.

9. The composition of claim 1, wherein said paradiamine ispara-aminodiphenolamine and said meta-aminophenol is2-carbamylmethylamino-4-hydroxy toluene.

10. The composition of claim 1, wherein said paradiamine is3,6-diamino-2,4-dimethy1 anisol dihydrochloride and saidmeta-amino-phenol is 2-amino-4-hydroxy toluene.

11. The composition of claim 1, wherein said paradiamine 15 paradiaminoanisol sulfate and said meta-aminophenol isZ-carbamylmethylamino-4-hydroxy toluene.

12. The composition of claim 1, wherein said paradiamine isparadiarnino-anisol sulfate and said meta-aminophenol is 2-(diethylcarbamyl)-l-methylamino-4-hydroxytoluene.

13. A method of dyeing hair which comprises the steps of applying adyeing amount of the composition of claim 1 to the hair, and thenrinsing, shampooing and drying the hair.

14. The method of claim 13 wherein said composition is mixed with anoxidizing agent just before being applied to the hair.

15. The method of claim 14 wherein said oxidizing agent is hydrogenperoxide.

16. The method of dyeing the hair which comprises the steps of applyingseparately thereto a dyeing amount 15 of an aqueous compositioncontaining an aromatic paradiamine having the formula in which R and Rare selected from the group consisting of hydrogen and methyl, but Rmust be methyl when R is methyl, and a composition containingmeta-amino-phenol which serves as a coupling substance having theformula in which R represents a substance selected from the groupconsisting of chlorine and hydrogen and R represents a substanceselected from the group consisting of hydrogen, carbamylmethyl, anddiethylcarbamylmethyl, but R is chlorine only when R is hydrogen andwherein the molar ratio of the aromatic paradiamine to saidmeta-amino-phenol is about 1 to 1.

17. The method of claim 16 with the step of applying a conventionaloxidizing agent to the hair.

References Cited UNITED STATES PATENTS 3,210,252 10/1965 Blanke et a1.167--88 FOREIGN PATENTS 983,207 2/1965 Great Britain 167-88 Ad. 14,1137/1911 France 81l (1st addition to No. 413,877) 1,145,746 3/1963 Germany167-88 30 ALBERT T. MEYERS, Primary Examiner L. SCHENKMAN, AssistantExaminer US. Cl. X.R.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION 3,59 ,3 3 DatedJuly 6 1971 Patent No.

Inventor(s) Gregoire Kalopissis and Andree Bugeut It is certified thaterror appears in the above-identified patent and that said LettersPatent are hereby corrected as shown below:

At Col. 1, between lines 15 and 245 001. 2, between lines 2 and 10; C01.8, between lines 15 2 (Claim 1); and

Col. 9, between lines 17 29 (Claim 16), change the structural formula toread Signed and sealed this 7th day of March 1972.

(SEAL) A ttesb:

EDWARD M.FLETCHER,JR. ROBERT GOTI'SCHALK 7 Commissioner of PatentsAttesting Officer USCOMM-DC 50376-P69 Q US GOVERNMENT PRINTING OFFICEI969 O-356'334 FORM PO-10SO (10-69)

